Crystal structure of 2,5 di­methyl 3 (3 methyl­phenyl­sulfon­yl) 1 benzo­furan

Crystal structure of

2,5-dimethyl-3-(3-methylphenylsulfonyl)-1-benzofuran

Hong Dae Choiaand Uk Leeb*

a_{Department of Chemistry, Dongeui University, San 24 Kaya-dong, Busanjin-gu,}

Busan 614-714, Republic of Korea, andb_{Department of Chemistry, Pukyong}

National University, 599-1 Daeyeon 3-dong, Nam-gu, Busan 608-737, Republic of Korea. *Correspondence e-mail: uklee@pknu.ac.kr

Received 7 August 2014; accepted 27 August 2014

Edited by L. Fabian, University of East Anglia, England

In the title compound, C17H16O3S, the dihedral angle between the plane of the benzofuran ring system [r.m.s. deviation = 0.010 (1) A˚ ] and that of the 3-methylphenyl ring is 79.09 (5)_. Intramolecular C—H O hydrogen bonds are observed. In the crystal, molecules are connected into a chain along thec -axis direction by two different pairs of inversion-generated interactions: C—H hydrogen bonds between the methyl groups and the benzene rings of the 3-methylphenyl fragments and–interactions between the benzene and furan rings of neighbouring molecules [centroid–centroid distance = 3.673 (2) A˚ ].

Keywords:crystal structure; benzofuran; 3-methylphenyl; C—H hydrogen bonds;–interactions.

CCDC reference:1021292

1. Related literature

For the pharmacological properties of compounds containing a benzofuran moiety, see: Aslam et al. (2009); Galal et al. (2009); Howlett et al. (1999); Khan et al. (2005); Ono et al. (2002). For natural products with a benzofuran ring, see: Akgul & Anil (2003); Soekamtoet al.(2003). For the synthesis of the starting material, 2,5-dimethyl-3-(3-methylphenyl-sulfanyl)-1-benzofuran, see: Choiet al. (1999). For a related structure, see: Choiet al.(2013).

2. Experimental

2.1. Crystal data

C17H16O3S

Mr= 300.36 Monoclinic,P21=n

a= 9.8769 (2) A˚

b= 11.3190 (2) A˚

c= 13.1320 (2) A˚ = 101.951 (1)

V= 1436.29 (4) A˚3

Z= 4

MoKradiation = 0.23 mm1

T= 173 K

0.330.290.23 mm

2.2. Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009)

Tmin= 0.927,Tmax= 0.947

13810 measured reflections 3589 independent reflections 2861 reflections withI> 2(I)

Rint= 0.035

2.3. Refinement R[F2_{> 2(F}2_{)] = 0.045}

wR(F2) = 0.128

S= 1.08 3589 reflections

193 parameters

H-atom parameters constrained max= 0.35 e A˚

3 min=0.39 e A˚ 3

Table 1

Hydrogen-bond geometry (A˚ ,_).

Cg1 is the centroid of the C11–C16 3-methylphenyl ring.

D—H A D—H H A D A D—H A

C10—H10C O3 0.98 2.34 3.078 (3) 131 C17—H17B Cg1i 0.98 2.88 3.478 (2) 121 Symmetry code: (i)xþ1;yþ1;zþ1.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction:SAINT; program(s) used to solve structure:SHELXS97(Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Bran-denburg, 1998); software used to prepare material for publication: SHELXL97.

Acknowledgements

The X-ray centre of the Gyeongsang National University is acknowledged for providing access to the single-crystal diffractometer.

data reports

Acta Cryst.(2014).E70, o1073–o1074 doi:10.1107/S1600536814019369 Choi and Lee

o1073

Supporting information for this paper is available from the IUCr electronic archives (Reference: FY2118).

References

Akgul, Y. Y. & Anil, H. (2003).Phytochemistry,63, 939–943.

Aslam, S. N., Stevenson, P. C., Kokubun, T. & Hall, D. R. (2009).Microbiol. Res.164, 191–195.

Brandenburg, K. (1998).DIAMOND. Crystal Impact GbR, Bonn, Germany. Bruker (2009).APEX2,SADABSandSAINT. Bruker AXS Inc., Madison,

Wisconsin, USA.

Choi, H. D., Seo, P. J. & Lee, U. (2013).Acta Cryst.E69, o817.

Choi, H. D., Seo, P. J. & Son, B. W. (1999).J. Korean Chem. Soc.43, 606–608. Farrugia, L. J. (2012).J. Appl. Cryst.45, 849–854.

Galal, S. A., Abd El-All, A. S., Abdallah, M. M. & El-Diwani, H. I. (2009).

Bioorg. Med. Chem. Lett.19, 2420–2428.

Howlett, D. R., Perry, A. E., Godfrey, F., Swatton, J. E., Jennings, K. H., Spitzfaden, C., Wadsworth, H., Wood, S. J. & Markwell, R. E. (1999).

Biochem. J.340, 283–289.

Khan, M. W., Alam, M. J., Rashid, M. A. & Chowdhury, R. (2005).Bioorg. Med. Chem.13, 4796–4805.

Ono, M., Kung, M. P., Hou, C. & Kung, H. F. (2002).Nucl. Med. Biol.29, 633– 642.

Sheldrick, G. M. (2008).Acta Cryst.A64, 112–122.

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Acta Cryst. (2014). E70, o1073–o1074 [doi:10.1107/S1600536814019369]

Crystal structure of 2,5-dimethyl-3-(3-methylphenylsulfonyl)-1-benzofuran

Hong Dae Choi and Uk Lee

S1. Comment

Molecules containing a benzofuran ring show interesting pharmacological properties such as antibacterial and antifungal,

antitumor and antiviral, antimicrobial activities (Aslam et al. 2009, Galal et al., 2009, Khan et al., 2005), and they are

potential inhibitors of β-amyloid aggregation (Howlett et al., 1999, Ono et al., 2002). These benzofuran compounds are

widely occurring in nature (Akgul & Anil, 2003; Soekamto et al., 2003). As a part of our ongoing program of

3-aryl-sulfonyl-2,5-dimethyl-1-benzofuran derivatives containing 4-methylphenylsulfonyl substituent in 3-position (Choi et al.,

2013), we report herein on the crystal structure of the title compound.

In the title molecule (Fig. 1), the benzofuran unit is essentially planar, with a mean deviation of 0.010 (1) Å from the

least-squares plane defined by the nine constituent atoms. The 3-methylphenyl ring is essentially planar, with a mean

deviation of 0.005 (1) Å from the least-squares plane defined by the six constituent atoms. The dihedral angle formed by

the benzofuran ring system and the 3-methylphenyl ring is 79.09 (5)°. In the crystal structure (Fig. 2), molecules are

linked along the c-axis direction by two different inversion-generated pairs of C–H···π hydrogen bonds (Table 1, Cg1 is

the centroid of the C11-C16 3-methylphenyl ring), and π–π interactions between the benzene and furan rings of

neighbouring molecules, with a Cg2···Cg3ii _{distance of 3.673 (2) Å and an interplanar distance of 3.570 (2) Å resulting in}

a slippage of 0.864 (2) Å (Cg2 and Cg3 are the centroids of the C2-C7 benzene ring and the C1/C2/C7/O1/C8 furan ring,

respectively). In addition, intramolecular C–H···O hydrogen bonds (Table 1) are observed .

S2. Experimental

The starting material 2,5-dimethyl-3-(3-methylphenylsulfanyl)-1-benzofuran was prepared by literature method (Choi et

al. 1999). 3-Chloroperoxybenzoic acid (77%, 515 mg, 2.3 mmol) was added in small portions to a stirred solution of

2,5-dimethyl-3-(3-methylphenylsulfanyl)-1-benzofuran (295 mg, 1.1 mmol) in dichloromethane (30 mL) at 273 K. After

being stirred at room temperature for 8h, the mixture was washed with saturated sodium bicarbonate solution (2 X 20

mL) and the organic layer was separated, dried over magnesium sulfate, filtered and concentrated at reduced pressure.

The residue was purified by column chromatography (hexane-ethyl acetate, 4:1 v/v) to afford the title compound as a

colorless solid [yield 73% (241 mg); m.p. 378-379 K; Rf = 0.43 (hexane-ethyl acetate, 4:1 v/v)]. Single crystals suitable

for X-ray diffraction were prepared by slow evaporation of a solution of the title compound (28 mg) in acetone (15 mL)

at room temperature.

S3. Refinement

All H atoms were positioned geometrically and refined using a riding model, with C–H = 0.95 Å for aryl and 0.98 Å for

methyl H atoms, Uiso (H) = 1.2Ueq (C) for aryl and 1.5Ueq (C) for methyl H atoms.The positions of methyl hydrogens were

Figure 1

The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the

50% probability level. H atoms are presented as small spheres of arbitrary radius.

Figure 2

A view of the C–H···O, C–H···π and π–π interactions (dotted lines) in the crystal structure of the title compound. H atoms

non-participating in hydrogen-bonding were omitted for clarity. [Symmetry codes: (i) - x + 1, - y + 1, - z + 1; (ii) - x + 1, -

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2,5-Dimethyl-3-(3-methylphenylsulfonyl)-1-benzofuran

Crystal data

C17H16O3S Mr = 300.36 Monoclinic, P21/n

Hall symbol: -P 2yn a = 9.8769 (2) Å b = 11.3190 (2) Å c = 13.1320 (2) Å β = 101.951 (1)° V = 1436.29 (4) Å3

Z = 4

F(000) = 632 Dx = 1.389 Mg m−3

Melting point = 378–379 K Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3458 reflections θ = 2.4–25.7°

µ = 0.23 mm−1 T = 173 K Block, colourless 0.33 × 0.29 × 0.23 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Radiation source: rotating anode Graphite multilayer monochromator Detector resolution: 10.0 pixels mm-1 φ and ω scans

Absorption correction: multi-scan

(SADABS; Bruker, 2009)

Tmin = 0.927, Tmax = 0.947

13810 measured reflections 3589 independent reflections 2861 reflections with I > 2σ(I) Rint = 0.035

θmax = 28.4°, θmin = 2.4° h = −13→12

k = −14→15 l = −17→17

Refinement

Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.045} wR(F2_{) = 0.128} S = 1.08 3589 reflections 193 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: difference Fourier map H-atom parameters constrained

w = 1/[σ2_(F

o2) + (0.0639P)2 + 0.4013P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.35 e Å−3

Δρmin = −0.39 e Å−3

Special details

Experimental. 1_{H NMR (δ p.p.m., CDCl3, 400 Hz): 7.77-7.83 (m, 2H), 7.67 (s, 1H), 7.34-7.41 (m, 2H), 7.29 (d, J = 8.56}

Hz, 1H), 7.10 (dd, J = 8.56 Hz and 1.72 Hz, 1H), 2.78 (s, 3H), 2.45 (s, 3H), 2.40 (s, 3H).

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance

matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> 2sigma(F}2_{) is}

used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 _{are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.}

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq

O2 0.20801 (13) 0.46348 (11) 0.14867 (10) 0.0366 (3) O3 0.24998 (14) 0.24951 (11) 0.13176 (10) 0.0384 (3) C1 0.45457 (18) 0.39515 (16) 0.14324 (12) 0.0287 (4) C2 0.52013 (17) 0.51022 (15) 0.14998 (12) 0.0273 (4) C3 0.48710 (18) 0.62452 (15) 0.17608 (13) 0.0297 (4) H3 0.4006 0.6408 0.1940 0.036* C4 0.58250 (19) 0.71390 (16) 0.17537 (13) 0.0306 (4) C5 0.70909 (19) 0.68878 (18) 0.14708 (14) 0.0356 (4) H5 0.7734 0.7511 0.1468 0.043* C6 0.74318 (19) 0.57618 (17) 0.11965 (14) 0.0361 (4) H6 0.8287 0.5597 0.1003 0.043* C7 0.64635 (19) 0.48979 (16) 0.12196 (13) 0.0306 (4) C8 0.54295 (19) 0.31645 (16) 0.11373 (13) 0.0315 (4) C9 0.5504 (2) 0.83842 (17) 0.20414 (15) 0.0385 (4) H9A 0.4861 0.8749 0.1458 0.058* H9B 0.6362 0.8845 0.2199 0.058* H9C 0.5082 0.8367 0.2654 0.058* C10 0.5398 (2) 0.18729 (17) 0.09586 (16) 0.0410 (5) H10A 0.6052 0.1485 0.1523 0.062* H10B 0.5660 0.1704 0.0293 0.062* H10C 0.4463 0.1574 0.0941 0.062* C11 0.33565 (18) 0.34750 (15) 0.31193 (14) 0.0293 (4) C12 0.3862 (2) 0.24005 (16) 0.35446 (15) 0.0350 (4) H12 0.3997 0.1762 0.3107 0.042* C13 0.4166 (2) 0.22735 (18) 0.46169 (15) 0.0405 (5) H13 0.4527 0.1549 0.4922 0.049* C14 0.3941 (2) 0.32033 (18) 0.52383 (15) 0.0383 (4) H14 0.4147 0.3104 0.5973 0.046* C15 0.34268 (18) 0.42744 (16) 0.48270 (14) 0.0321 (4) C16 0.31430 (18) 0.44131 (16) 0.37446 (14) 0.0306 (4) H16 0.2806 0.5146 0.3441 0.037* C17 0.3154 (2) 0.52658 (18) 0.55131 (15) 0.0387 (4) H17A 0.2158 0.5323 0.5488 0.058* H17B 0.3486 0.6009 0.5270 0.058* H17C 0.3641 0.5114 0.6230 0.058*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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C6 0.0315 (9) 0.0431 (11) 0.0355 (9) 0.0018 (8) 0.0109 (7) 0.0062 (8) C7 0.0340 (9) 0.0333 (10) 0.0247 (8) 0.0047 (8) 0.0064 (7) 0.0024 (7) C8 0.0349 (9) 0.0317 (10) 0.0268 (8) 0.0014 (8) 0.0035 (7) −0.0018 (7) C9 0.0408 (11) 0.0325 (10) 0.0415 (10) −0.0034 (8) 0.0066 (8) 0.0004 (8) C10 0.0458 (11) 0.0337 (11) 0.0427 (10) 0.0065 (9) 0.0075 (9) −0.0075 (8) C11 0.0277 (9) 0.0279 (9) 0.0330 (8) −0.0063 (7) 0.0078 (7) −0.0021 (7) C12 0.0384 (10) 0.0289 (10) 0.0391 (9) −0.0042 (8) 0.0112 (8) −0.0014 (8) C13 0.0472 (12) 0.0335 (11) 0.0416 (10) −0.0008 (9) 0.0115 (9) 0.0056 (8) C14 0.0392 (10) 0.0424 (11) 0.0348 (9) −0.0034 (9) 0.0110 (8) 0.0037 (8) C15 0.0263 (8) 0.0358 (10) 0.0357 (9) −0.0053 (7) 0.0098 (7) −0.0051 (8) C16 0.0282 (9) 0.0282 (9) 0.0359 (9) −0.0032 (7) 0.0079 (7) −0.0016 (7) C17 0.0403 (11) 0.0411 (11) 0.0363 (9) −0.0004 (9) 0.0115 (8) −0.0036 (8)

Geometric parameters (Å, º)

S1—O2 1.4324 (13) C9—H9B 0.9800 S1—O3 1.4364 (13) C9—H9C 0.9800 S1—C1 1.7399 (18) C10—H10A 0.9800 S1—C11 1.7693 (18) C10—H10B 0.9800 O1—C8 1.363 (2) C10—H10C 0.9800 O1—C7 1.380 (2) C11—C16 1.385 (2) C1—C8 1.359 (2) C11—C12 1.387 (3) C1—C2 1.449 (2) C12—C13 1.385 (3) C2—C7 1.390 (2) C12—H12 0.9500 C2—C3 1.394 (2) C13—C14 1.378 (3) C3—C4 1.384 (2) C13—H13 0.9500 C3—H3 0.9500 C14—C15 1.381 (3) C4—C5 1.405 (3) C14—H14 0.9500 C4—C9 1.510 (3) C15—C16 1.399 (2) C5—C6 1.385 (3) C15—C17 1.498 (3) C5—H5 0.9500 C16—H16 0.9500 C6—C7 1.372 (3) C17—H17A 0.9800 C6—H6 0.9500 C17—H17B 0.9800 C8—C10 1.480 (3) C17—H17C 0.9800 C9—H9A 0.9800

C3—C2—C1 136.45 (16) C13—C12—C11 118.97 (17) C4—C3—C2 118.84 (17) C13—C12—H12 120.5 C4—C3—H3 120.6 C11—C12—H12 120.5 C2—C3—H3 120.6 C14—C13—C12 119.69 (19) C3—C4—C5 119.88 (17) C14—C13—H13 120.2 C3—C4—C9 120.16 (17) C12—C13—H13 120.2 C5—C4—C9 119.95 (17) C13—C14—C15 122.04 (18) C6—C5—C4 122.18 (17) C13—C14—H14 119.0 C6—C5—H5 118.9 C15—C14—H14 119.0 C4—C5—H5 118.9 C14—C15—C16 118.42 (17) C7—C6—C5 116.23 (17) C14—C15—C17 121.33 (17) C7—C6—H6 121.9 C16—C15—C17 120.24 (17) C5—C6—H6 121.9 C11—C16—C15 119.54 (17) C6—C7—O1 125.76 (17) C11—C16—H16 120.2 C6—C7—C2 123.67 (18) C15—C16—H16 120.2 O1—C7—C2 110.56 (16) C15—C17—H17A 109.5 C1—C8—O1 110.60 (16) C15—C17—H17B 109.5 C1—C8—C10 134.37 (18) H17A—C17—H17B 109.5 O1—C8—C10 115.02 (16) C15—C17—H17C 109.5 C4—C9—H9A 109.5 H17A—C17—H17C 109.5 C4—C9—H9B 109.5 H17B—C17—H17C 109.5 H9A—C9—H9B 109.5

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Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the C11–C16 3-methylphenyl ring.

D—H···A D—H H···A D···A D—H···A

C10—H10C···O3 0.98 2.34 3.078 (3) 131 C17—H17B···Cg1i _{0.98 2.88 3.478 (2) 121}